JP6939553B2 - Resin composition - Google Patents

Description

The present invention relates to resin compositions. More specifically, the present invention relates to a resin composition preferably used for a surface protective film of a semiconductor element, an interlayer insulating film, an insulating layer of an organic electroluminescent element, and the like.

Conventionally, polyimide resins, polybenzoxazole resins, and polyamide-imide resins having excellent heat resistance and mechanical properties have been widely used as surface protective films and interlayer insulating films for semiconductor elements of electronic devices. When the coating films of the polyimide precursor, the polybenzoxazole precursor, and the polyamide-imide precursor are thermally dehydrated and ring-closed to obtain a thin film having excellent heat resistance and mechanical properties, high-temperature firing at about 350 ° C. is usually required.

In recent years, with the increasing integration of semiconductors, it has been required to reduce the heat load on semiconductor devices during the production process, and further, it has been required to reduce the warpage of the base wafer by increasing the thickness of the insulating material. Therefore, as a material required for the surface protective film and the interlayer insulating film, a cured film that can be cured by heat treatment at a low temperature of 250 ° C. or lower and that can reduce the generated stress on the base wafer can be obtained. A resin composition is required.

As a resin composition that can be cured by heat treatment at a low temperature, a method of introducing a flexible alkyl group, an alkylene glycol group, and a siloxane bond into a repeating unit of a resin such as an alkali-soluble closed ring polyimide or a polybenzoxazole precursor has been proposed. (Patent Documents 1 to 4).

Further, in order to obtain a cured film having high elongation and low stress, a resin composition containing a phenol resin having a long phenol skeleton, or a resin composition further containing polyimide or another resin in the phenol resin. A method using a thing has been proposed (Patent Document 5).

Further, in order to obtain a cured film having chemical resistance even by heat treatment at a low temperature, a method using a photosensitive resin composition containing a novolak resin having a crosslinkable group has been proposed (Patent Document 6).

Japanese Unexamined Patent Publication No. 2012-234030 Japanese Unexamined Patent Publication No. 2006-227063 JP-A-2009-175357 Japanese Unexamined Patent Publication No. 2008-224984 Japanese Unexamined Patent Publication No. 2012-252044 Japanese Unexamined Patent Publication No. 2011-197362

However, the closed ring polyimide having a flexible group as described in Patent Documents 1 to 4 has a problem that it is difficult to give sufficient mechanical properties to the cured film, although it can impart low stress property to the cured film. rice field.

Further, in the method using a resin composition as described in Patent Document 5, since the resin itself has poor crosslinkability, sufficient chemical resistance cannot be imparted to the cured film obtained even if a crosslinking agent is added. In addition, there is a problem that it is difficult to achieve both low stress and low stress.

Further, in the method using the photosensitive resin composition as described in Patent Document 6, the low stress property of the cured film obtained when the crosslinkability is too high becomes insufficient, and the substrate wafer warps when the thick film is formed. There was a problem that it was easy to grow.

Therefore, an object of the present invention is to provide a resin composition capable of obtaining a cured film having excellent chemical resistance, low stress resistance, and high elongation even in a heat treatment at a low temperature.

（一般式（１）中、Ｒ^１は、水素原子、ハロゲン原子、ニトロ基、シアノ基、脂肪族基、芳香族基、アセチル基、エステル基、アミド基、イミド基、ウレア基、またはチオウレア基のいずれかを有する有機基を表す。Ｘは、下記一般式（３）または（４）で表される有機基を表す。Ｒ^１およびＸが水素原子を有する場合、その水素原子はハロゲン原子、ニトロ基およびシアノ基のいずれかで置換されていてもよい。Ｙは架橋性基を表す。ａおよびｂは１以上の整数であり、ａ+ｂ≧６である。ａとｂの構造単位の配列はブロック的でもランダム的でもかまわない。ｍ、ｎ^１、およびｎ^２は１〜３の範囲内の整数である。ｑは０〜３の範囲内の整数である。）

（一般式（３）中、Ｒ^３、Ｒ^４、Ｒ^５およびＲ^６は、それぞれ独立に、炭素数１〜１０の脂肪族基を表し、水素原子またはフッ素で置換されていてもよい。また一般式（４）中、Ｒ^７、Ｒ^８、Ｒ^９およびＲ^１０は、それぞれ独立に、水素原子、アルキル基、フルオロアルキル基、シロキサン基、アルキルエーテル基、またはシロキサン基を表す。Ｚは、単結合、エーテル結合、ケトン基、カルボニル基、アミド基、またはスルホニル基のいずれかで表される２価の基である。）
The resin composition of the present invention has the following constitution. That is, (a) a phenol skeleton and a crosslinkable group having a group selected from the group consisting of a maleimide group, a nadic acid group, an acrylic group, an epoxy group, an alkoxymethyl group and a methylol group (hereinafter referred to as "crosslinkable group"). A resin composition containing a non-existent phenolic skeleton and containing an alkali-soluble resin having a weight average molecular weight in the range of 1,000 to 50,000.
The content ratio of the phenolic skeleton having the crosslinkable group in the total of 100 mol% of the structural units of the phenolic skeleton having the crosslinkable group and the phenolic skeleton not having the crosslinkable group is within the range of 5 to 90 mol%. and in the (a) alkali-soluble resin, have a structure represented by the general formula (1), the general formula a and b in (1), characterized by satisfying the relationship of a> b It is a resin composition.

(In the general formula (1), R ¹ is a hydrogen atom, a halogen atom, a nitro group, a cyano group, an aliphatic group, an aromatic group, an acetyl group, an ester group, an amide group, an imide group, a urea group, or a thiourea group. the .X represents an organic group having any one of, if .R ¹ and X represents an organic group represented by the following general formula (3) or (4) has a hydrogen atom, the hydrogen atom is a halogen atom, It may be substituted with either a nitro group or a cyano group. Y represents a cross-linking group. A and b are integers of 1 or more, and a + b ≧ 6. The sequence can be blocky or random. ^{M, n 1} , and n ² are integers in the range 1-3. Q is an integer in the range 0-3.)

(In the general formula (3), R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent an aliphatic group having 1 to 10 carbon atoms and may be substituted with a hydrogen atom or fluorine. In the general formula (4), R ⁷ , R ⁸ , R ⁹ and R ¹⁰ independently represent a hydrogen atom, an alkyl group, a fluoroalkyl group, a siloxane group, an alkyl ether group, or a siloxane group. Z represents a hydrogen atom, an alkyl group, a fluoroalkyl group, or a siloxane group. It is a divalent group represented by any one of a single bond, an ether bond, a ketone group, a carbonyl group, an amide group, or a sulfonyl group.)

According to the resin composition of the present invention, a cured film having excellent chemical resistance, low stress resistance, and high elongation can be obtained even by heat treatment at a low temperature.

It is a figure which showed the enlarged cross section of the pad part of the semiconductor device which has a bump. It is a figure which showed the detailed manufacturing method of the semiconductor device which has a bump.

The resin composition of the present invention comprises (a) a phenol skeleton having a crosslinkable group and a phenol skeleton not having a crosslinkable group, and an alkali having a weight average molecular weight in the range of 1,000 to 50,000. A resin composition containing a soluble resin and having the crosslinkable group, which accounts for 100 mol% of the total structural units of the phenolic skeleton having the crosslinkable group and the phenolic skeleton having no crosslinkable group. The content ratio of is in the range of 5 to 90 mol%. Further, it is preferable to contain one or more kinds of alkali-soluble resins selected from (b) polyimide precursor, polyamide-imide, polyimide, polybenzoxazole precursor, and polybenzoxazole. Further, it is preferable to contain (c) a photosensitizer and (d) a cross-linking agent. Each component may be abbreviated as (a) alkali-soluble resin, (b) alkali-soluble resin, (c) component, and (d) component, respectively.

According to the resin composition of the present invention, a cured film having excellent chemical resistance, low stress resistance, and high elongation can be obtained even by heat treatment at a low temperature of 250 ° C. or lower.

Alkali-soluble in the present invention means that it is dissolved in an alkaline aqueous solution such as tetramethylammonium hydroxide, choline, triethylamine, dimethylaminopyridine, monoethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide and sodium carbonate.

Further, the alkali-soluble resin (a) preferably has a structure represented by the general formula (1).

(In the general formula (1), R ¹ is a hydrogen atom, a halogen atom, a nitro group, a cyano group, an aliphatic group, an aromatic group, an acetyl group, an ester group, an amide group, an imide group, a urea group, or a thiourea group. the .X represents an organic group having any one of, if .R ¹ and X represents an organic group having an aliphatic group or an aromatic group has a hydrogen atom, the hydrogen atom is a halogen atom, a nitro group and a cyano group Y represents a cross-linking group. The cross-linking group means a functional group that can be cross-linked by a radical reaction, an addition reaction, a condensation reaction or the like. b is an integer of 1 or more, and a + b ≧ 6. The arrangement of the structural units of a and b may be blocky or random. M, n ¹ , and n ² are in the range of 1 to 3. Q is an integer in the range 0-3.)
The aliphatic group in R ¹ and X is preferably an organic group having at least one selected from an alkyl group, a fluoroalkyl group, an alkyl ether group and a siloxane group, and has an unsaturated bond and an alicyclic structure. May be good.

Is a cross-linkable group Y, a maleimide group, nadic acid, an acrylic group, an epoxy group, an alkoxymethyl group, a group selected from the group consisting of methylol group. Among these, an acrylic group or a group represented by the following general formula (2) is preferable from the viewpoint of pattern processability.

(R ² is a hydrogen atom, an aliphatic group, or an aromatic group.)
Further, from the viewpoint of improving the storage stability of the resin composition, it is preferable that Y is an alkoxymethyl group.

In the general formula (1), ^{preferred examples of R 1} are hydrogen atom, methyl group, halogen atom, trifluoromethyl group, nitro group, cyano group and acetyl group from the viewpoint of improving the alkali solubility of the resin composition. , Ester group, amide group, and imide group. Particularly preferred examples are a hydrogen atom and a methyl group.

Q in the general formula (1) is an integer in the range of 0 to 3, and is preferably 0 or 1 from the viewpoint of reactivity during polymer synthesis.

The X in the general formula (1) is preferably the following general formula (3) or (4).

(In the general formula (3), R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent an aliphatic group having 1 to 10 carbon atoms and may be substituted with a hydrogen atom or fluorine. In the general formula (4), R ⁷ , R ⁸ , R ⁹ and R ¹⁰ independently represent a hydrogen atom, an alkyl group, a fluoroalkyl group, a siloxane group, an alkyl ether group, or a siloxane group. Z represents a hydrogen atom, an alkyl group, a fluoroalkyl group, or a siloxane group. It is a divalent group represented by any one of a single bond, an ether bond, a ketone group, a carbonyl group, an amide group, or a sulfonyl group.)
Preferred examples of X in the general formula (1) include a p-xylylene group, a 4,4'-dimethylene biphenyl group, and a bis (4-methylenephenyl) ether group.

A and b in the general formula (1) are integers, respectively, and it is preferable that a + b ≧ 6 from the viewpoint of improving the toughness of the film after curing.

Further, a and b are preferably 1 or more, respectively, from the viewpoint of improving the toughness of the film after curing. Further, from the viewpoint of improving alkali solubility, each of a and b is preferably 1,000 or less, more preferably 100 or less, and particularly preferably 30 or less from the viewpoint of pattern processability.

Generally, increasing the ratio of crosslinkable groups contained in the resin can improve the chemical resistance of the obtained cured film, but on the other hand, the stress of the obtained cured film becomes large and warpage is likely to occur. Further, if the ratio of the crosslinkable group is lowered, the stress of the obtained cured film can be reduced, but the chemical resistance is lowered.

The alkali-soluble resin (a) of the present invention has both a phenol skeleton having a crosslinkable group and a phenol skeleton having no crosslinkable group. Therefore, it is possible to obtain a cured film that takes advantage of the chemical resistance effect of the crosslinkable group and the low stress effect of not having the crosslinkable group.

Further, it is preferable that a and b in the general formula (1) satisfy the relationship of a> b. By allowing a large number of phenol skeletons having no cross-linking group to exist, the effect of low stress in the cured film can be enhanced. As a result, it is possible to suppress the occurrence of warpage of the base wafer during the formation of a thick film in the manufacturing process of a semiconductor or the like.

Further, it is more preferable that a and b in the general formula (1) satisfy the relationship of 5 ≦ {b / (a + b)} × 100 ≦ 30. Here, "{b / (a + b)} x 100" is defined as the crosslinkable group introduction rate. By controlling a and b within this range, it is possible to further utilize both chemical resistance and low stress properties.

^{Further, n 1} in the general formula (1) is preferably 2 or 3. ^{The n 1} in the general formula (1) is preferably 2 or more from the viewpoint of improving alkali solubility and crosslinkability. On the other hand, from the viewpoint of improving the low stress property and heat resistance of the obtained cured film, n ¹ is preferably 3 or less.

The weight average molecular weight of the alkali-soluble resin (a) in the present invention is preferably 1,000 to 50,000. The weight average molecular weight is preferably 1,000 or more, and more preferably 3,000 or more, because high elongation can be obtained. Further, from the viewpoint of alkali solubility of the resin composition, it is preferably 50,000 or less, and more preferably 15,000 or less.

The weight average molecular weight in the present invention can be measured by gel permeation chromatography (GPC) and calculated from a calibration curve prepared using standard polystyrene.

Examples of the method for obtaining the (a) alkali-soluble resin include the method (I) or (II).

(I) A phenolic resin is obtained by polymerizing an aldehyde compound, a ketone compound, a methylol compound, an alkoxymethyl compound, a diene compound, or a haloalkyl compound as a condensing component with a phenol compound such as a phenol and a phenol derivative as shown below. Next, by introducing a crosslinkable group into a specific phenolic skeleton, an alkali-soluble resin having a phenolic skeleton having a crosslinkable group and a phenolic skeleton having no crosslinkable group can be obtained.

(II) By reacting a phenol compound with a non-excessive aldehyde in the presence of an alkaline catalyst, a phenol resin having a crosslinkable group of methylol introduced therein can be obtained.

Either of the above methods (I) and (II) may be used, but the method (I) may be used from the viewpoint of easy control of the introduction rate of the crosslinkable group and the abundance of types. preferable.
Further, in the method (I), from the viewpoint of (a) stability of the alkali-soluble resin and the resin composition, when the charged molar ratio of the phenol compound and the condensed component is set to 1, the phenol compound is set to 1. The condensed component is preferably in the range of 0.2 to 0.99, and more preferably in the range of 0.4 to 0.9.

(A) Examples of the phenolic compound that can be used to obtain an alkali-soluble resin include cresol, ethylphenol, propylphenol, butylphenol, amylphenol, cyclohexylphenol, hydroxybiphenyl, benzylphenol, nitrobenzylphenol, cyanobenzylphenol, and adamantanphenol. Xylenol, nitrophenol, fluorophenol, chlorophenol, bromophenol, trifluoromethylphenol, N- (hydroxyphenyl) -5-norbornene-2,3-dicarboxyimide, N- (hydroxyphenyl) -5-methyl-5 -Norbornene-2,3-dicarboxyimide, trifluoromethylphenol, hydroxybenzoic acid, methyl hydroxybenzoate, ethyl hydroxybenzoate, benzyl hydroxybenzoate, hydroxybenzamide, hydroxybenzaldehyde, hydroxyacetophenone, hydroxybenzophenone, hydroxybenzonitrile , Catecol, methylcatechol, ethylcatechol, hexylcatechol, benzylcatechol, nitrobenzylcatechol, resorcinol, methylresorcinol, ethylresorcinol, hexylresorcinol, benzylresorcinol, nitrobenzylresorcinol, hydroquinone, caffeic acid, dihydroxybenzoic acid, dihydroxybenzoic acid Methyl, ethyl dihydroxybenzoate, benzyl dihydroxybenzoate, dihydroxybenzamide, dihydroxybenzaldehyde, dihydroxyacetophenone, dihydroxybenzophenone, dihydroxybenzonitrile, N- (dihydroxyphenyl) -5-norbornene-2,3-dicarboxyimide, N- ( Dihydroxyphenyl) -5-methyl-5-norbornene-2,3-dicarboxyimide, nitrocatechol, fluorocatechol, chlorocatechol, bromocatechol, trifluoromethylcatechol, nitroresorcinol, fluororesorcinol, chlororesorcinol, bromoresorcinol, tri Fluoromethylresorcinol, pyrogallol, fluoroglucinol, 1,2,4-trihydroxybenzene, trihydroxybenzoic acid, methyl trihydroxybenzoate, ethyl trihydroxybenzoate, benzyl trihydroxybenzoate, trihydroxybenzamide, trihydroxybenz Al Examples thereof include dehydrate, trihydroxyacetophenone, trihydroxybenzophenone, and trihydroxybenzonitrile.

Examples of the aldehyde compound include acetaldehyde, propionaldehyde, pivalaldehyde, butylaldehyde, pentanal, hexanal, trioxane, glioxal, cyclohexylaldehyde, diphenylacetaldehyde, ethylbutylaldehyde, benzaldehyde, glyoxylic acid, 5-norbornene-2-carboxyaldehyde, and the like. Examples thereof include malondialdehyde, succindialdehyde, glutaaldehyde, salicylaldehyde, naphthoaldehyde, and terephthalaldehyde.

Examples of the ketone compound include acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone, dicyclohexyl ketone, dibenzyl ketone, cyclopentanone, cyclohexanone, bicyclohexanone, cyclohexanedione, 3-butin-2-one, 2-norbornanone, and adamantanone. , 2,2-Bis (4-oxocyclohexyl) propane and the like.

Examples of the methylol compound include 2,6-bis (hydroxymethyl) -p-cresol, 2,6-bis (hydroxymethyl) -4-ethylphenol, and 2,6-bis (hydroxymethyl) -4-propyl. Phenol, 2,6-bis (hydroxymethyl) -4-n-butylphenol, 2,6-bis (hydroxymethyl) -4-t-butylphenol, 2,6-bis (hydroxymethyl) -4-methoxyphenol, 2, , 6-bis (hydroxymethyl) -4-ethoxyphenol, 2,6-bis (hydroxymethyl) -4-propoxyphenol, 2,6-bis (hydroxymethyl) -4-n-butoxyphenol, 2,6- Bis (hydroxymethyl) -4-t-butoxyphenol, 1,3-bis (hydroxymethyl) urea, libitol, arabitol, alitol, 2,2-bis (hydroxymethyl) butyric acid, 2-benzyloxy-1,3- Propanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, monoacetin, 2-methyl-2-nitro-1,3-propanediol, 5-norbornen- 2,2-dimethanol, 5-norbornen-2,3-dimethanol, pentaerythritol, 2-phenyl-1,3-propanediol, trimethylolethane, trimethylolpropane, 3,6-bis (hydroxymethyl) durene , 2-Nitro-p-xylylene glycol, 1,10-dihydroxydecane, 1,12-dihydroxydodecane, 1,4-bis (hydroxymethyl) cyclohexane, 1,4-bis (hydroxymethyl) cyclohexene, 1,6 -Bis (hydroxymethyl) adamantan, 1,4-benzenedimethanol, 1,3-benzenedimethanol, 2,6-bis (hydroxymethyl) -p-cresol, 2,6-bis (hydroxymethyl) -1, 4-Dimethoxybenzene, 2,3-bis (hydroxymethyl) naphthalene, 2,6-bis (hydroxymethyl) naphthalene, 1,8-bis (hydroxymethyl) anthracene, 2,2'-bis (hydroxymethyl) diphenyl ether, 4,4'-bis (hydroxymethyl) diphenyl ether, 4,4'-bis (hydroxymethyl) diphenylthioether, 4,4'-bis (hydroxymethyl) benzophenone, 4-hydroxymethylbenzoic acid-4'-hydroxymethylphenyl , 4-hydro Xymethylbenzoic acid-4'-hydroxymethylanilide, 4,4'-bis (hydroxymethyl) phenylurea, 4,4'-bis (hydroxymethyl) phenylurethane, 1,8-bis (hydroxymethyl) anthracene, 4, 4'-bis (hydroxymethyl) biphenyl, 2,2'-dimethyl-4,4'-bis (hydroxymethyl) biphenyl, 2,2-bis (4-hydroxymethylphenyl) propane, ethylene glycol, diethylene glycol, triethylene Examples thereof include glycols, tetraethylene glycols, propylene glycols, dipropylene glycols, tripropylene glycols and tetrapropylene glycols.

Examples of the alkoxymethyl compound include 2,6-bis (methoxymethyl) -p-cresol, 2,6-bis (methoxymethyl) -4-ethylphenol, and 2,6-bis (methoxymethyl) -4-. Propylphenol, 2,6-bis (methoxymethyl) -4-n-butylphenol, 2,6-bis (methoxymethyl) -4-t-butylphenol, 2,6-bis (methoxymethyl) -4-methoxyphenol, 2,6-bis (methoxymethyl) -4-ethoxyphenol, 2,6-bis (methoxymethyl) -4-propoxyphenol, 2,6-bis (methoxymethyl) -4-n-butoxyphenol, 2,6 -Bis (methoxymethyl) -4-t-butoxyphenol, 1,3-bis (methoxymethyl) urea, 2,2-bis (methoxymethyl) butyric acid, 2,2-bis (methoxymethyl) -5-norbornen, 2,3-bis (methoxymethyl) -5-norbornen, 1,4-bis (methoxymethyl) cyclohexane, 1,4-bis (methoxymethyl) cyclohexene, 1,6-bis (methoxymethyl) adamantan, 1,4 -Bis (methoxymethyl) benzene, 1,3-bis (methoxymethyl) benzene, 2,6-bis (methoxymethyl) -p-cresol, 2,6-bis (methoxymethyl) -1,4-dimethoxybenzene, 2,3-bis (methoxymethyl) naphthalene, 2,6-bis (methoxymethyl) naphthalene, 1,8-bis (methoxymethyl) anthracene, 2,2'-bis (methoxymethyl) diphenyl ether, 4,4'- Bis (methoxymethyl) diphenyl ether, 4,4'-bis (methoxymethyl) diphenylthioether, 4,4'-bis (methoxymethyl) benzophenone, 4-methoxymethylbenzoic acid-4'-methoxymethylphenyl, 4-methoxymethyl Orthoperic acid-4'-methoxymethylanilide, 4,4'-bis (methoxymethyl) phenylurea, 4,4'-bis (methoxymethyl) phenylurethane, 1,8-bis (methoxymethyl) anthracene, 4,4 '-Bis (methoxymethyl) biphenyl, 2,2'-dimethyl-4,4'-bis (methoxymethyl) biphenyl, 2,2-bis (4-methoxymethylphenyl) propane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tri Ethylene glycol dimethyl ether, tetraethylene glycol dime Examples thereof include tyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol dimethyl ether, and tetrapropylene glycol dimethyl ether.

Examples of the diene compound include butadiene, pentadiene, hexadiene, heptadiene, octadiene, 3-methyl-1,3-butadiene, 1,3-butanediol-dimethacrate, 2,4-hexadiene-1-ol, and methylcyclohexadiene. , Cyclopentadiene, cyclohexadiene, cyclohexadiene, cyclooctadiene, dicyclopentadiene, 1-hydroxydicyclopentadiene, 1-methylcyclopentadiene, methyldicyclopentadiene, diallyl ether, diallyl sulfide, diallyl adipate, 2,5- Examples thereof include norbornadiene, tetrahydroindene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, triallyl cyanurate, diallyl isocyanurate, triallyl isocyanurate, diallylpropyl isocyanurate and the like.

Examples of the haloalkyl compound include xylene chloride, bischloromethyldimethoxybenzene, bischloromethyldurene, bischloromethylbiphenyl, bischloromethyl-biphenylcarboxylic acid, bischloromethyl-biphenyldicarboxylic acid, bischloromethyl-methylbiphenyl, and the like. Examples thereof include bischloromethyl-dimethylbiphenyl, bischloromethylanthracene, ethylene glycol bis (chloroethyl) ether, diethylene glycol bis (chloroethyl) ether, triethylene glycol bis (chloroethyl) ether, and tetraethylene glycol bis (chloroethyl) ether.

It is also possible to obtain a phenol resin by dehydrating, dealcoholizing, or polymerizing the phenol derivative while cleaving an unsaturated bond.

Moreover, you may use a catalyst at the time of polymerization. Examples of the catalyst used at the time of polymerization include an acidic catalyst and an alkaline catalyst.

Acidic catalysts include hydrochloric acid, sulfuric acid, nitrate, phosphoric acid, phosphite, methanesulfonic acid, p-toluenesulfonic acid, dimethylsulfate, diethylsulfate, acetic acid, oxalic acid, 1-hydroxyethylidene-1,1'-. Examples thereof include diphosphonic acid, zinc acetate, boron trifluoride, boron trifluoride / phenol complex, boron trifluoride / ether complex and the like.

As alkaline catalysts, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, triethylamine, pyridine, 4-N, N-dimethylaminopyridine, piperidine, piperazine, 1,4 -Diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [5,4,0] -7-undecene, 1,5-diazabicyclo [4,3,0] -5-nonen, ammonia, hexamethylenetetramine And so on.

Here, if the alkali metal contained in the alkaline catalyst is mixed in the resin composition, the insulating property is impaired, which is not preferable. Therefore, it is preferable to remove the metal salt catalyst by extracting with a solvent such as water after the solution of the phenol resin is obtained.

Details of the method for introducing a crosslinkable group into the phenol skeleton of the phenol resin include the following methods.

When the crosslinkable group is a methylol group, the phenol resin and aldehydes are reacted in the presence of an alkaline catalyst to obtain a resin containing a phenol skeleton having a crosslinkable group and a phenol skeleton having no crosslinkable group. Obtainable. When the crosslinkable group is an alkoxymethyl group, it can be further obtained by condensing a methylol group and an alcohol under acidic conditions.

Examples of the alcohol used for alkoxylation include monohydric alcohols having 1 to 4 carbon atoms, for example, methanol, ethanol, n-propanol, n-butanol, isobutanol, and alcohols substituted with aromatic groups. It is preferable to use methanol or ethanol because high reactivity can be obtained.

Further, an epoxy group or an acrylic group may be used as the crosslinkable group. Examples of the method for introducing these crosslinkable groups include a method of reacting a polyhydric phenol resin with epichlorohydrin, acryloyl chloride, and allyl chloride.

The amount of the crosslinkable group charged in the present invention is preferably 1 mol% or more and 100 mol% or less, and further 3 mol% or more and 50 mol% or less with respect to the phenol compound used for obtaining the phenol resin. Preferably, it is 5 mol% or more and 30 mol% or less, more preferably.

The introduction rate of the ^{crosslinkable group can be calculated by 1 1} H-NMR from the ratio of the peak of phenol and the peak of the crosslinkable group in the phenol resin.

An organic solvent can be used in the synthetic reaction of the alkali-soluble resin (a) of the present invention.

Specific examples of the organic solvent that can be used include bis (2-methoxyethyl) ether, methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, cyclohexanone, cyclopentanone, and the like. Examples thereof include, but are not limited to, toluene, xylene, γ-butyrolactone, N-methyl-2-pyrrolidone and the like.

The amount of the organic solvent used is preferably 10 to 1,000 parts by mass and more preferably 20 to 500 parts by mass with respect to 100 parts by mass of the total mass of the charged raw material excluding the organic solvent.

The reaction temperature is preferably 40 to 250 ° C, more preferably 100 to 200 ° C. The reaction time is preferably 1 to 10 hours.

Further, (a) the alkali-soluble resin may be a copolymer. In this case, as one of the copolymerization components, a compound having no phenolic hydroxyl group may be used in addition to the phenol compound.

The resin composition of the present invention preferably further contains (b) an alkali-soluble resin which is one or more selected from (b) polyimide precursor, polyamide-imide, polyimide, polybenzoxazole precursor, and polybenzoxazole.

The alkali-soluble resin (b) of the present invention includes polyamide, an acrylic polymer copolymerized with acrylic acid, a siloxane resin, a polyhydroxystyrene resin, and a crosslinkable group such as a methylol group, an alkoxymethyl group, an epoxy group, or an acrylic group. It is preferable that the resin is an alkali-soluble resin such as a resin in which the above-mentioned material is introduced and a copolymerization polymer thereof, and two or more kinds of these may be contained.

Since the alkali-soluble resin (a) contains a phenol skeleton having a crosslinkable group, it can be crosslinked with the alkali-soluble resin (b) to improve chemical resistance and heat resistance. On the other hand, since (a) the alkali-soluble resin also contains a phenolic skeleton having no crosslinkable group, (b) it is applied to the obtained cured film without impairing the original function of the resin contained in the alkali-soluble resin. Can be done.

Further, the alkali-soluble resin (b) preferably has at least one selected from an alkyl group, a fluoroalkyl group, an alkyl ether group, and a siloxane group. These organic groups may have an unsaturated bond or an alicyclic structure. As a result, flexibility and low elasticity can be imparted to the resin itself, so that the obtained cured film can be further imparted with high elongation and low stress.

The alkali-soluble resin (b) used in the present invention preferably has at least one of the structural units represented by the general formulas (5) to (8).

The general formula (5) is a structural unit of polyimide, the general formula (6) is a structural unit of polybenzoxazole, the general formula (7) is a structural unit of polyamideimide, and the general formula (8) is a polyimide precursor or polybenzoxazole. Each represents the structural unit of the precursor.

Examples of the polyimide precursor preferably used in the present invention include polyamic acid, polyamic acid ester, polyamic acid amide, and polyisoimide. For example, the polyamic acid can be obtained by reacting a tetracarboxylic acid, a corresponding tetracarboxylic acid dianhydride, a tetracarboxylic acid diester dichloride or the like with a diamine, a corresponding diisocyanate compound, or a trimethylsilylated diamine. The polyimide can be obtained, for example, by dehydrating and ring-closing the polyamic acid obtained by the above method by heating or chemical treatment with an acid or a base.

Examples of the polybenzoxazole precursor preferably used in the present invention include polyhydroxyamide. For example, the polyhydroxyamide can be obtained by reacting a bisaminophenol with a dicarboxylic acid, a corresponding dicarboxylic acid chloride, a dicarboxylic acid active ester, or the like. Polybenzoxazole can be obtained, for example, by dehydrating and closing the ring of the polyhydroxyamide obtained by the above method by heating or chemical treatment with a phosphoric acid anhydride, a base, a carbodiimide compound or the like.

The polyamide-imide precursor preferably used in the present invention can be obtained by reacting, for example, a tricarboxylic acid, a corresponding tricarboxylic acid anhydride, a tricarboxylic acid anhydride halide or the like with a diamine or diisocyanate. Polyamideimide can be obtained, for example, by dehydrating and ring-closing the precursor obtained by the above method by heating or chemical treatment with an acid or a base. Two or more kinds of resins having these structural units may be contained, or two or more kinds of structural units may be copolymerized. The alkali-soluble resin (a) in the present invention preferably contains 3 to 1000 structural units represented by the general formulas (5) to (8) in the molecule, and more preferably 20 to 200.

In the general formulas (5) to (8), R ¹¹ and R ¹⁴ are tetravalent organic groups, R ¹² , R ¹³ and R ¹⁶ are divalent organic groups, R ¹⁵ is a trivalent organic group, and R ¹⁷ is. A 2 to 4 valent organic group, R ¹⁸ represents a 2 to 12 valent organic group. All of R ^{11 to} R ¹⁸ are preferably those having an aromatic ring and an aliphatic ring. R ¹⁹ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. r represents an integer of 0 to 2, and s represents an integer of 0 to 10.

In the general formulas (5) to (8), R ¹¹ is a tetracarboxylic acid derivative residue, R ¹⁴ is a dicarboxylic acid derivative residue, R ¹⁵ is a tricarboxylic acid derivative residue, and R ¹⁷ is a di-, tri- or tetra-. Represents a carboxylic acid derivative residue. Examples of the acid components constituting R ¹¹ , R ¹³ , R ¹⁵ and R ¹⁷ include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, naphthalenedicarboxylic acid, bis (carboxyphenyl) propane and biphenyldicarboxylic acid. Aromatic dicarboxylic acids such as benzophenone dicarboxylic acid and triphenyldicarboxylic acid, cyclobutanedicarboxylic acid, cyclohexanedicarboxylic acid, malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetra Fluoroscusic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutar Acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, octafluoroadipic acid, pimeric acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosveric acid, azelaic acid, sebacic acid, hexadecafluorosevacinic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, Tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecandioic acid, eicosanedioic acid, heneicosanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedi Trimerit as an example of tricarboxylic acids such as acids, heptacosandioic acid, octacosandioic acid, nonakosandioic acid, triacontanedioic acid, gentriaconttandioic acid, dotriacontanedioic acid, and aliphatic dicarboxylic acids such as diglycolic acid. Examples of acids, trimesic acids, diphenyl ether tricarboxylic acids, biphenyl tricarboxylic acids, and tetracarboxylic acids are pyromellitic acid, 3,3', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4'-biphenyl. Tetracarboxylic acid, 2,2', 3,3'-biphenyltetracarboxylic acid, 3,3', 4,4'-benzophenonetetracarboxylic acid, 2,2', 3,3'-benzophenonetetracarboxylic acid, 2 , 2-bis (3,4-dicarboxyphenyl) hexafluoropropane, 2,2-bis (2,3-dicarboxyphenyl) hexafluoropropane, 1,1-bis (3) , 4-Dicarboxyphenyl) ethane, 1,1-bis (2,3-dicarboxyphenyl) ethane, bis (3,4-dicarboxyphenyl) methane, bis (2,3-dicarboxyphenyl) methane, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) ether, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2 , 3,5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid and other aromatic tetracarboxylic acids, butanetetracarboxylic acid, 1,2-dimethyl-1,2,3, 4-Cyclobutanetetracarboxylic acid, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 3,4-dicarboxy -1,2,3,4-tetrahydro-1-naphthalene succinic acid, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid, 2,3,5 -Tricarboxy-2-cyclopentaneacetic acid, bicyclo [2,2,2] octo-7-en-2,3,5,6-tetracarboxylic acid, 2,3,4,5-tetracarboxylic acid, 3 , 5,6-Tricarboxy-2-norbornan Acetic acid alicyclic tetracarboxylic acid 1,3,3a, 4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] Semi-lipocyclic tetracarboxylic acid dianhydrides such as furan-1,3-dione, and some of the hydrogen atoms of these aromatic rings and hydrocarbons have 1 to 10 carbon atoms. Those substituted with alkyl groups, fluoroalkyl groups, halogen atoms, etc., -S-, -SO-, -SO _2- , -NH-, -NCH _3- , -N (CH ₂ CH ₃ )-, Derived from those containing bonds such as ―N (CH ₂ CH ₂ CH ₃ ) ―, −N (CH (CH ₃ ) ₂ ) ―, −COO―, −CONH―, —OCONH―, or −NHCONH― The structure and the like can be mentioned.

Of these, in the general formula (8), when r is 1 or 2, one or two carboxyl groups of the tricarboxylic acid and the tetracarboxylic acid each correspond to ^{19 COOR groups.} These acid components can be used as they are, or as acid anhydrides, active esters and the like. Further, these two or more kinds of acid components may be used in combination.

In the general formulas (5) to (8), R ¹² , R ¹⁴ , R ¹⁶ and R ¹⁸ represent diamine residues. As ^{an example of the diamine component constituting R 12} , R ¹⁴ , R ¹⁶ and R ¹⁸ , it is preferable to include an organic group derived from a diamine having an aliphatic group.

A diamine having an aliphatic group is preferable because it is excellent in flexibility and elasticity, and can contribute to low stress and high elongation by lowering the elastic modulus.

Examples of the diamine containing an aliphatic group include a diamine having at least one selected from an alkyl group which may have an unsaturated bond or an alicyclic structure, a fluoroalkyl group, an alkyl ether group and a siloxane group.

Specifically, it is a diamine selected from at least one of an alkyl group, a cycloalkyl group, an alkyl ether group, a cycloalkyl ether group, and a siloxane group, and a part of hydrogen atoms of these hydrocarbons has 1 to 1 carbon atoms. It may be substituted with an alkyl group of 10, a fluoroalkyl group, a halogen atom, etc., and may be substituted with -S-, -SO-, -SO _2- , -NH-, -NCH _3- , -N (CH ₂ CH ₃ ). -, -N (CH ₂ CH ₂ CH ₃ )-,-N (CH (CH ₃ ) ₂ )-, -COO-, -CONH-, -OCONH-, or -NHCONH- even if it contains a bond. Often, these organic groups may have an unsaturated bond or an alicyclic structure.

Specific compounds of diamine having an aliphatic group include bis (3-aminopropyl) tetramethyldisiloxane, bis (p-amino-phenyl) octamethylpentasiloxane, ethylenediamine, and 1,3-diamino as diamine components. Propane, 2-methyl-1,3-propanediamine, 1,4-diaminobutane, 1,5-diaminopentane, 2-methyl-1,5-diaminopentane, 1,6-diaminohexane, 1,7-diamino Heptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-Cyclohexanediamine, 1,2-bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 4,4'-methylenebis (cyclohexylamine) , 4,4'-Methylenebis (2-methylcyclohexylamine), 1,2-bis (2-aminoethoxy) ethane, KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR- 176, D-200, D-400, D-2000, THF-100, THF-140, THF-170, RE-600, RE-900, RE-2000, RP-405, RP-409, RP-2005, RP-2009, RT-1000, HE-1000, HT-1100, HT-1700, (the above trade names, manufactured by HUNTSMAN Co., Ltd.) can be mentioned. Further, the following compounds may be mentioned, and some of the hydrogen atoms of these aromatic rings and hydrocarbons may be substituted with alkyl groups having 1 to 10 carbon atoms, fluoroalkyl groups, halogen atoms and the like. S-, -SO-, -SO _2- , -NH-, -NCH _3- , -N (CH ₂ CH ₃ )-, -N (CH ₂ CH ₂ CH ₃ )-, -N (CH (CH ₃₎ ) ₂ ) -, -COO-, -CONH-, -OCONH-, or -NHCONH- may be included.

(In the formula, n ₃ , n ₄ , n ₅ , n ₆ , and n ₇ are integers of 1 to 20, respectively.)
The diamine having a aliphatic group of the present invention is an organic group having at least one selected from an alkyl group and an alkyl ether group, and these are those having an acyclic structure in which the main chain is a straight chain. However, it is preferable because flexibility and elasticity can be obtained, and low stress and high elongation can be achieved when the cured film is formed. Among these, the alkyl ether group is particularly preferable because it has a high elasticity and therefore has a large effect of increasing the elongation.

Further, it is more preferable that the alkyl ether diamine residue having an aliphatic group has a structural unit represented by the general formula (9).

(In the general formula (9), R ^{20 to} R ²³ each independently represent an alkylene group having 2 to 10 carbon atoms, and n ₈ , n ₉ , and n _{10 are 1 ≦ n 3} ≦ 20, 0 ≦, respectively. It _{represents an integer in the range of n 4} ≤ 20, 0 ≤ n ₅ ≤ 20, and the sequence of repeating units may be blocky or random. In the general formula (9), * indicates a chemical bond.)
In the structural unit represented by the general formula (9), high elongation can be imparted when a cured film is formed due to the elasticity of the ether group. Further, due to the presence of the ether group, complex formation or hydrogen bonding with the metal can be performed, and high adhesion to the metal can be obtained.

Examples of the compound having a structural unit represented by the general formula (9) include 1,2-bis (2-aminoethoxy) ethane, KH-511, ED-600, ED-900, ED-2003, EDR-148, and so on. EDR-176, D-200, D-400, D-2000, THF-100, THF-140, THF-170, RE-600, RE-900, RE-2000, RP-405, RP-409, RP- Examples thereof include 2005, RP-2009, RT-1000, HE-1000, HT-1100, HT-1700, (trade name, manufactured by HUNTSMAN Corporation), and compounds represented by the following formulas. Some of the hydrogen atoms of these aromatic rings and hydrocarbons may be substituted with alkyl groups having 1 to 10 carbon atoms, fluoroalkyl groups, halogen atoms, etc., and may be substituted with —S—, —SO—, —SO. _2- , -NH-, -NCH _3- , -N (CH ₂ CH ₃ )-, -N (CH ₂ CH ₂ CH ₃ )-, -N (CH (CH ₃ ) ₂ )-, -COO-, It may include, but is not limited to, a bond such as —CONH—, —OCONH—, or —NHCONH—.

(In the formula, n ₅ , n ₆ , and n ₇ are integers of 1 to 20.)
The number average molecular weight of the structural unit represented by the general formula (9) is preferably 150 or more and 2,000 or less. The number average molecular weight of the structural unit represented by the general formula (9) is preferably 150 or more, more preferably 600 or more, still more preferably 900 or more, because flexibility and elasticity can be obtained. Further, the number average molecular weight of the structural unit represented by the general formula (9) is preferably 2,000 or less, more preferably 1,800 or less, and more preferably 1,800 or less because the solubility in an alkaline solution can be maintained. More preferably 500 or less.

Further, the diamine having an aliphatic group preferably has a structure having no phenolic hydroxyl group. Since it does not have a phenolic hydroxyl group, shrinkage due to ring closure or dehydration can be suppressed, and low stress properties can be imparted to the cured film.

By using a diamine having such an aliphatic group, it is possible to impart low stress property, high elongation property, and high metal adhesion to the obtained cured film while maintaining solubility in an alkaline solution. can.

The content of the diamine residue having an aliphatic group of the present invention is preferably 5 to 40 mol% in the total diamine residue. When it is contained in an amount of 5 mol% or more, the effect of high metal adhesion due to the diamine residue having an aliphatic group can be obtained, and when it is contained in an amount of 40 mol% or less, the hygroscopicity of the resin is lowered. It is preferable because it can prevent peeling and a cured film having high reliability can be obtained.

The sequence of repeating units of diamine residues having an aliphatic group may be blocky or random. Since high metal adhesion and low stress can be imparted and elongation is improved, the sequence of repeating units of diamine residues having an aliphatic group is R ^18- (OH) s of the general formula (8). It is preferable to include the structural unit represented by.

R ¹² , R ¹⁴ , R ¹⁶ and R ¹⁸ preferably further contain a diamine residue having an aromatic ring. By having a diamine residue having an aromatic ring, the heat resistance of the obtained cured film can be improved.

Specific examples of the diamine having an aromatic ring include, for example, bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, and bis (3-amino-). 4-Hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) methylene, bis (3-amino-4-hydroxyphenyl) ether, bis (3-amino-4-hydroxy) biphenyl, bis (3-amino) -4-Hydroxyphenyl) fluorene, 2,2'-bis (trifluoromethyl) -5,5'-dihydroxybenzidine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'- Diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 1,4 -Bis (4-aminophenoxy) benzene, benzine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-) Aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl} ether, 1,4-bis (4-aminophenoxy) benzene, 2,2'-dimethyl-4 , 4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diamino Biphenyl, 2,2', 3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3', 4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-bis (Trifluoromethyl) -4,4'-diaminobiphenyl and other aromatic diamines and some of the hydrogen atoms of these aromatic rings and hydrocarbons can be used as alkyl groups, fluoroalkyl groups, or halogens with 1 to 10 carbon atoms. Examples and examples thereof include compounds substituted with atoms and the like, diamines having the structures shown below, and the like, but the present invention is not limited thereto. The other diamine to be copolymerized can be used as it is or as a corresponding diisocyanate compound, trimethylsilylated diamine. Further, these two or more kinds of diamine components may be used in combination.

^{R 11 to} R ¹⁸ in the general formulas (5) to (8) can contain a phenolic hydroxyl group, a sulfonic acid group, a thiol group and the like in the skeleton. By using a resin having an appropriate phenolic hydroxyl group, sulfonic acid group or thiol group, a resin composition having an appropriate alkali solubility can be obtained.

Further, (b) it is preferable to have a fluorine atom in the structural unit of the alkali-soluble resin. Fluorine atoms impart water repellency to the surface of the film during alkaline development, and can suppress penetration from the surface.

The fluorine atom content in the (b) alkali-soluble resin is preferably 10% by mass or more when the (b) alkali-soluble resin is 100% by mass in order to sufficiently obtain the effect of preventing the penetration of the interface, and the content is preferably 10% by mass or more with respect to the alkaline aqueous solution. From the viewpoint of solubility, 20% by mass or less is preferable.

These diamines can be used as is or as the corresponding diisocyanate compound, trimethylsilylated diamine. Further, these two or more kinds of diamine components may be used in combination. For applications where heat resistance is required, it is preferable to use 50 mol% or more of the total amount of aromatic diamine.

Further, in order to improve the storage stability of the resin composition, (b) an end-capping agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound at the main chain end of the alkali-soluble resin. It is preferable to seal with. The introduction ratio of the monoamine used as the terminal encapsulant is preferably 0.1 mol% or more, particularly preferably 5 mol% or more, preferably 60 mol% or less, and particularly preferably 50, based on the total amine components. It is less than mol%. The introduction ratio of the acid anhydride, monocarboxylic acid, monoacid chloride compound or monoactive ester compound used as the terminal encapsulant is preferably 0.1 mol% or more, particularly preferably 5 mol% with respect to the diamine component. The above is preferably 100 mol% or less, and particularly preferably 90 mol% or less. A plurality of different end groups may be introduced by reacting a plurality of end sealants.

Examples of monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-. Hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-amino Naphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-amino Aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid , 3-Amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like are preferable. Two or more of these may be used.

Acid anhydrides such as acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds include phthalic acid anhydride, maleic anhydride, nadic acid anhydride, cyclohexanedicarboxylic acid anhydride, and 3-hydroxyphthalic acid anhydride. Compounds, 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene , 1-Mercapto-7-carboxynaphthalene, 1-Mercapto-6-carboxynaphthalene, 1-Mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid and other monocarboxylic acids and their carboxyls. Monoic chloride compounds with acid chloride groups, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 2, A monoacid chloride compound in which only one carboxyl group of a dicarboxylic acid such as 6-dicarboxynaphthalene is acid chloride, a monoacid chloride compound and N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboxy An active ester compound obtained by reacting with an imide is preferable. Two or more of these may be used.

Further, (a) the terminal sealant introduced into the alkali-soluble resin can be easily detected by the following method. For example, a resin into which an end-capping agent has been introduced is dissolved in an acidic solution, decomposed into an amine component and an acid anhydride component, which are constituent units, and this is measured by gas chromatography (GC) or NMR. The end-capping agent used in the present invention can be easily detected. Apart from this, the resin component into which the terminal encapsulant has been introduced can also be easily detected by ^{directly measuring with a pyrolysis gas chromatograph (PGC) or an infrared spectrum and a 13 C-NMR spectrum.}

In the resin having the structural unit represented by any of the general formulas (5) to (7), the number of repetitions of the structural unit is preferably 3 to 1000, and more preferably 3 to 200. Further, in the resin having the structural unit represented by the general formula (8), the number of repetitions of the structural unit is preferably 10 or more and 1000 or less. Within this range, a thick film can be easily formed.

The alkali-soluble resin (b) used in the present invention may be composed of only the structural units represented by any of the general formulas (5) to (8), or may be a copolymer with other structural units. Alternatively, it may be a mixture. At that time, the structural unit represented by any of the general formulas (5) to (8) is preferably contained in an amount of 10 mol% or more, more preferably 30 mol% or more, based on the total amount of the alkali-soluble resin (b). Among these, from the viewpoint of heat resistance and storage stability during low-temperature firing, it is preferable that the structural unit of the general formula (5) is contained in the molecule in an amount of 10 mol% to 100 mol%, and more preferably 30 to 100 mol%. preferable. The type and amount of structural units used for copolymerization or mixing are preferably selected within a range that does not impair the mechanical properties of the cured film obtained by the final heat treatment. Examples of such a main clavicle include benzimidazole and benzothiazole.

The content of the (b) alkali-soluble resin is preferably 1 to 1000 parts by mass with respect to 100 parts by mass of the (a) alkali-soluble resin. More preferably, it is 20 to 150 parts by mass. Within this range, a cured film having (a) alkali-soluble resin and (b) alkali-soluble resin does not become excessively crosslinked, has low stress and high elongation, and has chemical resistance. It is preferable because it can be obtained.

Further, the resin composition of the present invention preferably contains (c) a photosensitizer.

(C) As the photosensitive agent, the resin composition containing a photoacid generator can be used as a positive photosensitive resin composition (positive photosensitive varnish). Further, the resin composition containing the photopolymerizable compound can be a negative type photosensitive resin composition (negative type photosensitive varnish).

Examples of the positive photoacid generator include a quinonediazide compound, a sulfonium salt, a phosphonium salt, a diazonium salt, and an iodonium salt. Among them, the quinone diazide compound is preferably used because it exhibits an excellent dissolution inhibitory effect and can obtain a photosensitive resin composition having high sensitivity and low film reduction. Further, two or more kinds of photosensitizers may be contained. Thereby, the ratio of the dissolution rate of the exposed portion and the unexposed portion can be further increased, and a highly sensitive photosensitive resin composition can be obtained.

The quinonediazide compound includes a polyhydroxy compound in which quinonediazide sulfonic acid is ester-bonded, a polyamino compound in which quinonediazide sulfonic acid is conjugated with a sulfonamide, and a polyhydroxypolyamino compound in which quinonediazide sulfonic acid is ester-bonded and / or sulfone. Examples thereof include amide-bonded compounds. All the functional groups of these polyhydroxy compounds and polyamino compounds may not be substituted with quinonediazide, but it is preferable that 50 mol% or more of all the functional groups are substituted with quinonediazide. By using such a quinone diazide compound, a positive photosensitive resin composition that reacts with i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) of a mercury lamp, which is a general ultraviolet ray, can be obtained. Obtainable.

In the present invention, as the quinone diazide compound, either a 5-naphthoquinone diazidosulfonyl group or a 4-naphthoquinone diazidosulfonyl group is preferably used. Compounds having both of these groups in the same molecule may be used, or compounds using different groups may be used in combination.

The quinone diazide compound used in the present invention is synthesized from a specific phenol compound by the following method. For example, a method of reacting 5-naphthoquinonediazidesulfonyl chloride with a phenol compound in the presence of triethylamine can be mentioned. Examples of the method for synthesizing the phenol compound include a method of reacting an α- (hydroxyphenyl) styrene derivative with a polyhydric phenol compound under an acid catalyst.

The content of (c) the photosensitizer is preferably 3 to 40 parts by mass with respect to 100 parts by mass of (a) alkali-soluble resin. By setting the content of the photosensitizer within this range, higher sensitivity can be achieved. Further, a sensitizer or the like may be contained as needed.

The resin composition of the present invention preferably contains (d) a thermal cross-linking agent.

Examples of the thermal cross-linking agent include an acrylic group, an epoxy group, an alkoxymethyl group, and a methylol group. Among them, a compound having at least two alkoxymethyl groups or methylol groups is preferable from the viewpoint of stability. By having at least two of these groups, a crosslinked structure can be formed by a condensation reaction with a resin and a homologous molecule. When used in combination with a photoacid generator or photopolymerization initiator, a wider range of designs is possible to improve sensitivity, chemical resistance of cured films, and elongation.

Examples of the thermal cross-linking agent having an epoxy group include epoxy group-containing agents such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polymethyl (glycidyloxypropyl) siloxane, and silicone. However, the present invention is not limited thereto. Specifically, "Epicron" (registered trademark) 850-S, Epicron HP-4032, Epicron HP-7200, Epicron HP-820, Epicron HP-4700, Epicron EXA-4710, Epicron HP-4770, Epicron EXA-859CRP. , Epicron EXA-1514, Epicron EXA-4880, Epicron EXA-4850-150, Epicron EXA-4850-1000, Epicron EXA-4816, Epicron EXA-4822 (trade name, manufactured by Dainippon Ink and Chemicals Co., Ltd.), Examples thereof include Rica Resin BEO-60E (hereinafter, trade name, Shin Nihon Rika Co., Ltd.), EP-4003S, EP-4000S (Adeca Co., Ltd.) and the like.

Examples of having an alkoxymethyl group or a methylol group include, for example, DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DMLBisOCHP-Z, DML-BPC, DML-BisOC-P, DMOM-PC, DMOM-PTBP, DMOM- MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM- BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (trade name, manufactured by Honshu Kagaku Kogyo Co., Ltd.), "NIKALAC" (registered trademark) MX-290 , NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, NIKALAC MX-750LM (trade name, manufactured by Sanwa Chemical Co., Ltd.). Two or more of these may be contained. Among these, when HMOM-TPHAP and MW-100LM are added, the crosslink density is improved and the chemical resistance is improved, which is preferable.

The content of the (d) thermal cross-linking agent is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and more preferably 5 parts by mass or more with respect to 100 parts by mass of the (a) alkali-soluble resin. .. Further, it is preferably 50 parts by mass or less, more preferably 25 parts by mass or less. Within this range, it is preferable because the effect of low stress can be obtained while improving the chemical resistance by forming a crosslinked structure having a high crosslink rate by condensation reaction with the resin and the same type of molecule.

The resin composition of the present invention may further contain a thermoacid generator. The thermoacid generator generates an acid by heating, (a) promotes the cross-linking reaction of the alkali-soluble resin, promotes the cyclization of the unclosed ring imide ring and the oxazole ring, and heat resistance and chemical resistance of the cured film. The sex can be further improved.

Further, if necessary, a small molecule compound having a phenolic hydroxyl group may be contained within a range that does not reduce the shrinkage residual film ratio after curing. As a result, the development time can be shortened.

Examples of these compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, and BisP-. CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP , BIR-BIPC-F (above, trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.) and the like. Two or more of these may be contained.

The content of the small molecule compound having a phenolic hydroxyl group is preferably 1 to 40 parts by mass with respect to 100 parts by mass of the (a) alkali-soluble resin.

The resin composition of the present invention preferably contains a solvent. Examples of the solvent include polar aprotonic solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide and dimethylsulfoxide, tetrahydrofuran, dioxane and propylene glycol monomethyl ether. Ethers such as propylene glycol monoethyl ether, ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate and the like. Examples thereof include esters, alcohols such as ethyl lactate, methyl lactate, diacetone alcohol, 3-methyl-3-methoxybutanol, aromatic hydrocarbons such as toluene and xylene, and the like. Two or more of these may be contained.

The content of the solvent in the present invention is preferably 100 to 1500 parts by mass with respect to 100 parts by mass of (a) alkali-soluble resin.

The resin composition of the present invention may contain a photopolymerizable compound.

The photopolymerizable compound that imparts negative-type photosensitivity to the resin composition of the present invention contains a polymerizable unsaturated functional group. Examples of the polymerizable unsaturated functional group include unsaturated double bond functional groups such as vinyl group, allyl group, acryloyl group and methacryloyl group, and / also unsaturated triple bond functional groups such as propargyl. Among these, a group selected from a conjugated vinyl group, an acryloyl group and a methacryloyl group is preferable in terms of polymerizability. Further, the number of the functional groups contained is preferably 1 to 4 from the viewpoint of stability, and the respective groups do not have to be the same. Further, the photopolymerizable compound referred to here preferably has a molecular weight of 30 to 800. When the molecular weight is in the range of 30 to 800, the compatibility with the polyamide is good and the stability of the resin composition solution is good.

Preferred photopolymerizable compounds include, for example, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylpropandiacrylate, trimethylol. Propanetriacrylate, trimethylolpropanedimethacrylate, trimethylolpropanetrimethacrylate, styrene, α-methylstyrene, 1,2-dihydronaphthalene, 1,3-diisopropenylbenzene, 3-methylstyrene, 4-methylstyrene, 2 -Vinylnaphthalene, butyl acrylate, butyl methacrylate, isobutyl acrylate, hexyl acrylate, isooctyl acrylate, isobornyl acrylate, isobornyl methacrylate, cyclohexyl methacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate , Neopentyl glycol diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate Methacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecanediacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate , 2-Hydroxyethyl acrylate, 2-Hydroxyethyl methacrylate, 1,3-diacryloyloxy-2-hydroxypropane, 1,3-dimethacryloyloxy-2-hydroxypropane, methylenebisacrylamide, N, N-dimethylacrylamide, N-methylol acrylamide, 2,2,6,6-tetramethylpiperidinyl methacrylate, 2,2,6,6-tetramethylpiperidinyl acrylate, N-methyl-2,2,6,6-tetramethylpi Peridinyl methacrylate, N-methyl-2,2,6,6-tetramethylpiperidinyl acrylate, ethylene oxide modified bisphenol A diacrelate G, ethylene oxide-modified bisphenol A dimethacrylate, N-vinylpyrrolidone, N-vinylcaprolactam and the like. These are used alone or in combination of two or more.

Of these, particularly preferred are 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecanediacrylate, isobornyl acrylate, isobornyl methacrylate, pentaerythritol triacrylate, and penta. Elythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, methylenebisacrylamide, N, N-dimethylacrylamide, N-methylolacrylamide, 2,2,6,6- Tetramethylpiperidinyl methacrylate, 2,2,6,6-tetramethylpiperidinyl acrylate, N-methyl-2,2,6,6-tetramethylpiperidinyl methacrylate, N-methyl-2,2,6 , 6-Tetramethylpiperidinyl acrylate, ethylene oxide-modified bisphenol A diacrylate, ethylene oxide-modified bisphenol A dimethacrylate, N-vinylpyrrolidone, N-vinylcaprolactam and the like.

The content of the photopolymerizable compound in the resin composition of the present invention is preferably 5 to 200 parts by mass with respect to 100 parts by mass of the alkali-soluble resin (a), and 5 to 150 parts by mass from the viewpoint of compatibility. Is more preferable. By setting the content of the photopolymerizable compound to 5 parts by mass or more, elution of the exposed portion during development can be prevented, and a resin composition having a high residual film ratio after development can be obtained. Further, by setting the content of the photopolymerizable compound to 200 parts by mass or less, whitening of the film at the time of film formation can be suppressed.

The viscosity of the resin composition of the present invention is preferably 2 to 5000 mPa · s. By adjusting the solid content concentration so that the viscosity is 2 mPa · s or more, it becomes easy to obtain a desired film thickness. On the other hand, when the viscosity is 5000 mPa · s or less, it becomes easy to obtain a highly uniform coating film. A resin composition having such a viscosity can be easily obtained, for example, by setting the solid content concentration to 5 to 60% by mass.

The resin composition of the present invention contains a surfactant, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, alcohols such as ethanol, cyclohexanone, and methyl isobutyl ketone for the purpose of improving wettability with a substrate, if necessary. It may contain ketones such as, and ethers such as tetrahydrofuran and dioxane.

Further, the resin composition of the present invention may contain inorganic particles. Preferred specific examples include, but are not limited to, silicon oxide, titanium oxide, barium titanate, alumina, talc and the like. The primary average particle size of these inorganic particles is preferably 100 nm or less and 60 nm or less. The individual particle diameters of the inorganic particles were measured with a scanning electron microscope (scanning electron microscope manufactured by JEOL Ltd., JSM-6301NF). The average particle size can be calculated by measuring the diameters of 100 particles randomly selected from photographs and obtaining the arithmetic mean thereof.

Further, in order to enhance the adhesiveness to the substrate, trimethoxyaminopropylsilane, trimethoxyepoxysilane, trimethoxyvinylsilane, trimethoxythiolpropyl as silicon components in the resin composition of the present invention within a range that does not impair storage stability. It may contain a silane coupling agent such as silane. The preferable content is (a) 0.01 to 5 parts by mass with respect to 100 parts by mass of the alkali-soluble resin.

Next, a method of forming a relief pattern of a cured film using the resin composition of the present invention will be described.

First, the resin composition of the present invention is applied to a substrate. As the substrate, silicon wafers, ceramics, gallium arsenide, wafers formed of metals such as copper and aluminum, wafers formed of sealing resins such as epoxy resins, substrates, and the like are used, but are not limited thereto. As a coating method, there are methods such as rotary coating using a spinner, slit nozzle, spray coating, and roll coating. The coating film thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, and the like, but is usually applied so that the film thickness after drying is 0.1 to 150 μm. When it is made into a resin sheet, it is then dried and peeled off. The resin sheet of the present invention is a sheet in which the resin composition of the present invention is applied onto a support, dried at a temperature and time within a range in which the solvent can be volatilized, and is not cured. Refers to those in a state of being soluble in an aqueous solution. The resin sheet of the present invention can also be made into a resin sheet by following the above-mentioned production method using the resin composition.

In order to enhance the adhesiveness between the substrate such as a silicon wafer and the resin composition, the substrate can also be pretreated with the above-mentioned silane coupling agent. For example, a solution in which a silane coupling agent is dissolved in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and diethyl adipate in an amount of 0.5 to 20% by mass is prepared. Surface treatment by spin coating, dipping, spray coating, steam treatment, etc. In some cases, heat treatment is then performed at 50 ° C. to 300 ° C. to allow the reaction between the substrate and the silane coupling agent to proceed.

Next, the substrate on which the resin composition or the resin sheet is applied or laminated is dried to obtain a resin film. Drying is preferably carried out in the range of 50 ° C. to 150 ° C. for 1 minute to several hours using an oven, a hot plate, infrared rays or the like.

Next, the resin composition film is irradiated with chemical rays through a mask having a desired pattern and exposed. Chemical rays used for exposure include ultraviolet rays, visible rays, electron beams, X-rays, etc., but in the present invention, i-rays (wavelength 365 nm), h-rays (wavelength 405 nm), and g-rays (wavelength 436 nm) of mercury lamps are used. Is preferable.

To form a relief pattern on the cured film, after exposure, the exposed area is removed with a developer. The developing solution includes tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, and dimethyl. An aqueous solution of an alkaline compound such as aminoethyl methacrylate, cyclohexylamine, ethylenediamine and hexamethylenediamine is preferable. In some cases, these alkaline aqueous solutions are mixed with polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, γ-butyrolactone and dimethylacrylamide, methanol, ethanol, etc. Alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutyl ketone may be added alone or in combination of several types. good. After development, it is preferable to rinse with water. Here, too, alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water for rinsing.

After development, a temperature of 150 ° C. to 500 ° C. is applied to proceed the thermal cross-linking reaction to improve heat resistance and chemical resistance. This heat treatment is carried out for 5 minutes to 5 hours while selecting a temperature and gradually raising the temperature, or selecting a certain temperature range and continuously raising the temperature. As an example, heat treatment is performed at 130 ° C. and 200 ° C. for 30 minutes each. Alternatively, a method such as linearly raising the temperature from room temperature to 400 ° C. over 2 hours can be mentioned. The curing conditions in the present invention are preferably 150 ° C. or higher and 350 ° C. or lower, but 160 ° C. or higher and 250 ° C. or lower are more preferable because the present invention provides a cured film particularly excellent in low temperature curability.

The relief pattern of the cured film formed by the resin composition of the present invention is suitably used for applications such as a passivation film for semiconductors, a protective film for semiconductor elements, and an interlayer insulating film for multilayer wiring for high-density mounting. Examples of electronic devices having a surface protective film, an interlayer insulating film, and the like obtained by using the resin composition of the present invention include MRAM having low heat resistance. That is, the resin composition of the present invention is suitable for the surface protective film of MRAM. In addition to MRAM, polymer memory (PFRAM) and phase change memory (PCRAM, or Ovonics Unified Memory: OUM), which are promising next-generation memories, are also more heat-resistant than conventional memories. It is likely to use low new materials. Therefore, the resin composition of the present invention is also suitable for these surface protective films. Further, a display device including a first electrode formed on the substrate and a second electrode provided facing the first electrode, specifically, for example, an LCD, an ECD, an ELD, or an organic electroluminescent element. It can be used for an insulating layer such as the display device (organic electroluminescent device) used. In particular, in recent years, semiconductor device electrodes, multilayer wiring, and circuit board wiring have become mainstream in semiconductor devices having copper electrodes, copper wiring, and bumps due to further miniaturization of the structure, and etching of copper and barrier metal. , When forming the pattern of the resist, it is in a state of being in contact with many chemicals such as flux. When the relief pattern of the cured film formed by the resin composition of the present invention is used as a protective film for such electrodes and wiring, it is particularly preferably used because it has high resistance to those chemicals.

Next, an application example of the resin composition of the present invention to a semiconductor device having bumps will be described with reference to the drawings. FIG. 1 is an enlarged cross-sectional view of a pad portion of a semiconductor device having bumps. As shown in FIG. 1, in the silicon wafer 1, a passivation film 3 is formed on an Al pad 2 for input / output, and a via hole is formed in the passivation film 3. Further, an insulating film 4 formed by using the resin composition of the present invention is formed on the insulating film 4, and a metal film 5 made of Cr, Ti or the like is formed so as to be connected to the Al pad 2. Each pad is insulated by etching the periphery of the solder bump 10 of the metal film 5. A barrier metal 8 and a solder bump 10 are formed on the insulated pad. When the soft component is introduced into the resin composition, the warp of the wafer is small, so that exposure and wafer transportation can be performed with high accuracy. In addition, since polyimide resin and polybenzoxazole resin have excellent mechanical properties, stress from the sealing resin can be relaxed even during mounting, which prevents damage to the low-k layer and provides a highly reliable semiconductor device. can.

Next, a detailed method for producing a semiconductor device will be described. In the step 2a of FIG. 2, the resin composition of the present invention is applied onto the silicon wafer 1 on which the Al pad 2 and the passivation film 3 are formed, and the patterned insulating film 4 is formed through the photolithography step. Then, in the step 2b, the metal film 5 is formed by a sputtering method. As shown in 2c of FIG. 2, a metal wiring 6 is formed on the metal film 5 by a plating method. Next, as shown in 2d'of FIG. 2, the resin composition of the present invention is applied, and the insulating film 7 is formed as a pattern as shown in 2d of FIG. 2 through a photolithography step. At this time, the resin composition of the insulating film 7 is subjected to thick film processing on the scribe line 9. Wiring (so-called rewiring) can be further formed on the insulating film 7. When forming a multi-layer wiring structure having two or more layers, by repeating the above steps, rewiring of two or more layers is separated by an interlayer insulating film obtained from the resin composition of the present invention. The structure can be formed. At this time, the formed insulating film comes into contact with various chemicals a plurality of times, but the insulating film obtained from the resin composition of the present invention is excellent because it has excellent adhesion and chemical resistance. A multi-layer wiring structure can be formed. There is no upper limit to the number of layers in the multi-layer wiring structure, but those with 10 or less layers are often used.

Next, as shown in 2e and 2f of FIG. 2, the barrier metal 8 and the solder bump 10 are formed. Then, dicing along the scribe line 9 is performed to cut each chip. If the insulating film 7 does not have a pattern formed on the scribe line 9 or if a residue remains, cracks or the like occur during dicing, which affects the reliability of the chip. Therefore, it is very preferable to be able to provide pattern processing excellent in thick film processing as in the present invention in order to obtain high reliability of the semiconductor device.

The resin composition of the present invention is also suitably used for a fan-out wafer level package (fan-out WLP). In the fan-out WLP, an expansion portion is provided around the semiconductor chip using a sealing resin such as epoxy resin, rewiring is performed from the electrode on the semiconductor chip to the expansion portion, and a solder ball is also mounted on the expansion portion. It is a semiconductor package that secures the required number of terminals. In the fan-out WLP, wiring is installed so as to straddle the boundary line formed by the main surface of the semiconductor chip and the main surface of the sealing resin. That is, an interlayer insulating film is formed on a base material made of two or more kinds of materials such as a semiconductor chip with metal wiring and a sealing resin, and wiring is formed on the interlayer insulating film. In addition to this, in a type of semiconductor package in which a semiconductor chip is embedded in a recess formed in a glass epoxy resin substrate, wiring is installed so as to straddle the boundary line between the main surface of the semiconductor chip and the main surface of the printed circuit board. .. Also in this embodiment, an interlayer insulating film is formed on a base material made of two or more kinds of materials, and wiring is formed on the interlayer insulating film. The cured film obtained by curing the resin composition of the present invention has high adhesion to a semiconductor chip to which metal wiring is applied and also has high adhesion to a sealing resin to an epoxy resin or the like, so that there are two or more types. It is suitably used as an interlayer insulating film provided on a base material made of the above material.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. First, the evaluation method in each Example and Comparative Example will be described. For the evaluation, a resin composition (hereinafter referred to as varnish) filtered with a 1 μm polytetrafluoroethylene filter (manufactured by Sumitomo Electric Industries, Ltd.) was used.

(1) Weight average molecular weight measurement (a) For the molecular weight of the alkali-soluble resin, use a GPC (gel permeation chromatography) device Waters2690-996 (manufactured by Japan Waters Co., Ltd.) and use N-methyl-2-pyrrolidone as the developing solvent. It was measured as (hereinafter referred to as NMP), and the weight average molecular weight (Mw) was calculated in terms of polystyrene.

(2) Calculation of crosslinkable group introduction rate (a) The content ratio of the phenol skeleton having a crosslinkable group in the alkali-soluble resin was defined as the crosslinkable group introduction rate. The value (unit:%) obtained by multiplying "b / (a + b)", which is the crosslinkable group introduction rate, by 100, was measured by the following method. A 400 MHz, ¹ H-NMR (nuclear magnetic resonance) device (AL-400 manufactured by JEOL Ltd.) was used for the measurement. First, (a) the alkali-soluble resin was measured in a deuterated chloroform solution 16 times. Based on the integral value of the proton (chemical shift = 4.80 ppm) of −CH ₂ − in the alkoxymethyl-CH ₂ OR and the integral value of the proton (chemical shift = 5.35 ppm) of the phenol group, cross-linking is performed by the following equation. The sex group introduction rate was calculated.

Further, for epichlorohydrin and allyl chloride which directly react with the hydroxyl group of phenol and become an epoxy group or an acrylic group, the crosslinkable group introduction rate was calculated by the following formula.

(3) Evaluation of chemical resistance Varnish was applied on a 6-inch silicon wafer. Using a coating and developing apparatus Mark-7, the film thickness after prebaking at 120 ° C. for 3 minutes was adjusted to 11 μm. A spin coating method was used as the coating method. After prebaking, the temperature is raised to 200 ° C. at 3.5 ° C./min at an oxygen concentration of 20 ppm or less using an inert oven CLH-21CD-S (manufactured by Koyo Thermo System Co., Ltd.), and heat treatment is performed at 200 ° C. for 1 hour. Was done. When the temperature became 50 ° C. or lower, the wafer was taken out, the film thickness was measured, and then the wafer was immersed in a solvent of dimethyl sulfoxide (DMSO) for 100 minutes at 70 ° C. After washing the wafer taken out of the solvent with pure water, the film thickness is measured again, and the absolute value of the rate of change exceeds 15% or the cured film is peeled off is insufficient (D), within 15%. Those exceeding 10% were regarded as acceptable (C), those within 10% and exceeding 5% were regarded as good (B), those within 5% were regarded as better (A).

(4) Evaluation of stress (low stress property)
The varnish was applied on a silicon wafer by a spin coating method using a coating developer ACT-8 so that the film thickness after prebaking at 120 ° C. for 3 minutes was 10 μm, and the varnish was prebaked. Then, using an inert oven CLH-21CD-S, the temperature was raised to 220 ° C. at an oxygen concentration of 20 ppm or less at a heating rate of 3.5 ° C. per minute under a nitrogen stream, and heat treatment was performed at 220 ° C. for 1 hour. .. When the temperature became 50 ° C. or lower, the silicon wafer was taken out, and the stress of the cured film was confirmed with a stress measuring device FLX2908 (manufactured by KLA Tencor). The result was insufficient (D) when it was 30 MPa or more, acceptable (B) when it was 20 MPa or more and less than 30 MPa, and good (A) when it was less than 20 MPa.

(5) Elongation evaluation (high elongation)
The varnish was applied and prebaked on an 8-inch silicon wafer by a spin coating method using a coating developer ACT-8 so that the film thickness after prebaking at 120 ° C. for 3 minutes was 11 μm. Then, using an inert oven CLH-21CD-S (manufactured by Koyo Thermo System Co., Ltd.), the temperature was raised to 220 ° C. at 3.5 ° C./min at an oxygen concentration of 20 ppm or less, and heat treatment was performed at 220 ° C. for 1 hour. rice field. When the temperature became 50 ° C. or lower, the wafer was taken out and immersed in 45% by mass of hydrofluoric acid for 5 minutes to peel off the film of the resin composition from the wafer. This film is cut into strips having a width of 1 cm and a length of 9 cm, and using Tencilon RTM-100 (manufactured by Orientec Co., Ltd.), the tensile speed is 50 mm / at room temperature of 23.0 ° C. and humidity of 45.0% RH. It was pulled in minutes and the elongation at the break point was measured. The measurement was performed on 10 strips per sample, and the average value of the top 5 points was calculated from the results. The value of breaking point elongation is very good when the breaking point elongation value is 60% or more (A), 40% or more and less than 60% is acceptable (B), 20% or more and less than 40%. Those with less than 20% were regarded as acceptable (C), and those with less than 20% were regarded as insufficient (D).

Synthesis Example 1 (A-1) Resin A flask equipped with a thermometer, a dropping funnel, a cooling tube, and a stirrer is purged with nitrogen gas while (0-1) novolak resin EP-4080G (trade name, Asahi Organic Materials Co., Ltd.). Mw = 10,600), 45 g (0.5 mol) of epichlorohydrin, and 370 g of dimethyl sulfoxide were charged and dissolved. After the temperature was raised to 65 ° C., the pressure was reduced to an azeotropic pressure, and 90 g (1.1 mol) of a 49% aqueous sodium hydroxide solution was added dropwise over 5 hours. Then, stirring was continued for 0.5 hours under the same conditions. During this period, the distillate distilled off by azeotrope was separated by a Dean-Stark trap, the aqueous layer was removed, and the reaction was carried out while returning the oil layer to the reaction system. Then, unreacted epichlorohydrin and dimethyl sulfoxide were distilled off by vacuum distillation. To the obtained crude epoxy resin, 500 mL of gamma-butyrolactone was added and dissolved. Further, 10 g of a 10% aqueous sodium hydroxide solution was added to this solution and reacted at 80 ° C. for 2 hours, and then washing with 150 g of water was repeated 3 times until the pH of the washing solution became neutral. Next, the inside of the system was dehydrated by azeotrope, and after undergoing microfiltration, the solvent was distilled off under reduced pressure to obtain a (A-1) resin solution containing an epoxy group and having a solid content concentration of 50%. The Mw was 12,000 and the crosslinkable group introduction rate was 45%.

Synthesis Example 2 (A-2) Resin Nitrogen-substituted three-necked flask 1,000 ml contains 108.0 g of m-cresol, 108.0 g of methanol, and 40.0 g of sodium hydroxide, and the temperature is raised to 67 ° C. with stirring. After that, a reflux reaction was carried out for 30 minutes. Then, the reaction solution was cooled to 40 ° C., 53 g of 92% by mass paraformaldehyde was charged, the temperature was raised to 67 ° C. again, and the reflux reaction was carried out for 5 hours. After completion of the reaction, the reaction solution was cooled to 30 ° C. or lower, and 140.0 g of 30 mass% sulfuric acid was added dropwise over 30 minutes so that the reaction solution did not reach 35 ° C. or higher. The pH of the obtained reaction solution was 4.9. Further, 540.0 g of ion-exchanged water was added to the reaction solution, and the mixture was stirred for 20 minutes and allowed to stand for 20 minutes, and then the separated aqueous layer was removed. Methyl isobutyl ketone (MIBK) 216.0 g and ion-exchanged water 324.0 g, which are wash separation solvents, were added to the reaction solution, and the mixture was stirred at 30 ° C. for 20 minutes and allowed to stand for 20 minutes to remove the separated aqueous layer. Further, 324.0 g of ion-exchanged water was added, and the washing operation was repeated until the electrical conductivity of the removed water became 100 μScm or less. After the washing was completed, 300 g of γ-butyrolactone was added, and ion-exchanged water and MIBK were distilled off at 70 ° C. and a pressure of 0.08 MPa to obtain a (A-2) resin solution having a solid content of 50% by mass. The Mw was 3000 and the crosslinkable group introduction rate was 85%.

Synthesis Example 3 (A-3) Resin (0-3) MEH-7851M (trade name, manufactured by Meiwakasei Workers, Mw = 2,400), which is a phenol / biphenylene resin, is dissolved in 300 mL of methanol, and 2 g of sulfuric acid is added. The mixture was stirred at room temperature for 24 hours. 15 g of an anion type ion exchange resin (Amberlist IRA96SB manufactured by Rohmand Haas) was added to this solution, and the mixture was stirred for 1 hour, and the ion exchange resin was removed by filtration. Then, 500 mL of gamma-butyrolactone was added, and methanol was removed by a rotary evaporator to prepare a (A-3) resin solution having a solid content of 50% by mass. The Mw was 11,000 and the crosslinkable group introduction rate was 35%.

Synthesis Example 4 (A-4) Pyrogallol 50.4 g (0.4 mol), 4,4'-bis (methoxymethyl) biphenyl 72. 7 g (0.3 mol), 2.1 g (0.15 mol) of diethyl sulfuric acid, and 27 g of diethylene glycol dimethyl ether were mixed and stirred at 70 ° C. to dissolve the solid substance. The mixed solution was heated to 120 ° C. in an oil bath, and the generation of methanol was confirmed from the reaction solution. The reaction solution was stirred as it was at 120 ° C. for 2 hours. Next, the reaction vessel was cooled in the air, and 100 g of tetrahydrofuran was separately added thereto and stirred. The reaction diluent was added dropwise to 4 L of water under high-speed stirring to disperse and precipitate the resin, which was recovered, washed with water as appropriate, dehydrated, and then vacuum-dried to obtain a phenol resin (0-4).
Next, the phenol resin (0-4) was dissolved in a solution in which 80 g (2.0 mol) of sodium hydroxide was dissolved in 800 g of pure water. After complete dissolution, 36 g of a 37 mass% formalin aqueous solution was added dropwise at 25 ° C. over 2 hours. Then, the mixture was stirred at 25 ° C. for 17 hours. 98 g of sulfuric acid was added thereto for neutralization, and the mixture was left as it was for 2 days. The white solid formed in the solution after being left to stand was washed with 100 mL of water. The white solid was vacuum dried at 50 ° C. for 48 hours.
Next, the resin thus obtained was dissolved in 300 mL of methanol, 2 g of sulfuric acid was added, and the mixture was stirred at room temperature for 24 hours. 15 g of an anion type ion exchange resin (Amberlist IRA96SB manufactured by Rohmand Haas) was added to this solution, and the mixture was stirred for 1 hour, and the ion exchange resin was removed by filtration. Then, 500 mL of gamma-butyrolactone was added, and methanol was removed by a rotary evaporator to prepare a (A-4) resin solution having a solid content of 50% by mass. The Mw was 11,000 and the crosslinkable group introduction rate was 25%.

Synthesis Example 5 (A-5) Resin Nitrogen-substituted three-necked flask 1,000 ml contains 108.0 g of m-cresol, 108.0 g of methanol, and 40.0 g of sodium hydroxide, and the temperature is raised to 67 ° C. with stirring. After that, a reflux reaction was carried out for 30 minutes. Then, the reaction solution was cooled to 40 ° C., 300 g of 92% by mass paraformaldehyde was charged, the temperature was raised to 67 ° C. again, and the reflux reaction was carried out for 5 hours. After completion of the reaction, the reaction solution was cooled to 30 ° C. or lower, and 140.0 g of 30 mass% sulfuric acid was added dropwise over 30 minutes so that the reaction solution did not reach 35 ° C. or higher. The pH of the obtained reaction solution was 4.9. Further, 540.0 g of ion-exchanged water was added to the reaction solution, and the mixture was stirred for 20 minutes and allowed to stand for 20 minutes, and then the separated aqueous layer was removed. Methyl isobutyl ketone (MIBK) 216.0 g and ion-exchanged water 324.0 g, which are wash separation solvents, were added to the reaction solution, and the mixture was stirred at 30 ° C. for 20 minutes and allowed to stand for 20 minutes to remove the separated aqueous layer. Further, 324.0 g of ion-exchanged water was added, and the washing operation was repeated until the electrical conductivity of the removed water became 100 μScm or less. After the washing was completed, 300 g of γ-butyrolactone was added, and ion-exchanged water and MIBK were distilled off at 70 ° C. and a pressure of 0.08 MPa to obtain a resin solution having a solid content of 50% by mass. The Mw of the obtained (A-5) resin solution was 3000, and the crosslinkable group introduction rate was 120%.

Synthesis Example 6 (A-6) Resin Acryloyl was added to a solution of phenol resin (0-4) obtained in the same manner as in Synthesis Example 4 and 80 g (2.0 mol) of sodium hydroxide in 800 g of tetrahydrofuran. After adding 30 mL (0.4 mol) of chloride and attaching a reflux tube, the reaction was carried out in an oil bath at 70 ° C. for 4 hours. The solution after the reaction was naturally filtered and the solution was evaporated.
The residual solution was dissolved in 30 mL of chloroform and the solution was transferred to a separatory funnel. 50 ml of water was added thereto for washing. Extraction was performed with chloroform three times, sodium sulfate was added to the obtained chloroform solution, the mixture was left overnight, and then cotton filtration was performed. The product was recovered after evaporation of the resulting solution. Then, 500 mL of gamma-butyrolactone was added to prepare a (A-6) resin solution having a solid content of 50% by mass. The Mw was 11,000 and the crosslinkable group introduction rate was 30%.

Synthesis Example 7 Alkali-soluble resin (B-1)
To a mixed solution containing 500 ml of tetrahydrofuran and 0.01 mol of sec-butyllithium as an initiator, a total of 20 g of pt-butoxystyrene and styrene was added at a molar ratio of 3: 1 and polymerized with stirring for 3 hours. I let you. The polymerization termination reaction was carried out by adding 0.1 mol of methanol to the reaction solution. The reaction mixture was then poured into methanol to purify the polymer and the precipitated polymer was dried to give a white polymer. Further, the white polymer is dissolved in 400 ml of acetone, a small amount of concentrated hydrochloric acid is added at 60 ° C., the mixture is stirred for 7 hours, and then poured into water to precipitate the polymer, and pt-butoxystyrene is deprotected to hydroxystyrene. After conversion, washing and drying, a purified p-hydroxystyrene-styrene copolymer (B-1) was obtained. (B-1) had a weight average molecular weight (Mw) of 3,500 as analyzed by GPC.

Synthesis Example 8 Alkali-soluble resin (B-2)
Under dry nitrogen airflow, BAHF 29.30 g (0.08 mol), 1,3-bis (3-aminopropyl) tetramethyldisiloxane 1.24 g (0.005 mol), 4-aminophenol as end-capping agent 3.27 g (0.03 mol) (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 80 g of NMP. To this, 31.2 g (0.1 mol) of bis (3,4-dicarboxyphenyl) ether dianhydride (hereinafter referred to as ODPA, manufactured by Manac Inc.) was added together with 20 g of NMP, and the mixture was stirred at 200 ° C. for 5 hours. .. After completion of stirring, the solution was poured into 3 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 80 ° C. for 20 hours to obtain an alkali-soluble polyimide resin (B-2) powder. As a result of evaluation by the above method, it was estimated that the weight average molecular weight of the resin (B-2) was 25,000 and the imidization rate was 100%.

Synthesis Example 9 Alkali-soluble resin (B-3)
According to Synthesis Example 1, BAHF (34.79 g, 0.095 mol), PBOM (31.53 g, 0.088 mol), 1,3-bis (3-aminopropyl) tetramethyldisiloxane (1.24 g, 0.0050 mol), 5-norbornene-2,3-dicarboxylic acid anhydride (3.94 g, 0.024 mol), acetic acid (52.82 g, 0.50 mol), NMP352 g. A powder of soluble polyamide resin (B-3) was obtained. As a result of evaluation by the above method, the weight average molecular weight of the resin (B-3) was 35,800.

Synthesis Example 10 Alkali-soluble resin (B-4)
Under a dry nitrogen stream, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (hereinafter referred to as BAHF) (27.47 g, 0.075 mol) was dissolved in 257 g of NMP. To this, 1,1'-(4,4'-oxybenzoyl) imidazole (hereinafter referred to as PBOM) (17.20 g, 0.048 mol) was added together with 20 g of NMP, and the mixture was reacted at 85 ° C. for 3 hours. Subsequently, RT-1000 (20.00 g, 0.020 mol) containing propylene oxide and tetramethylene ether glycol structure, 1,3-bis (3-aminopropyl) tetramethyldisiloxane (1.24 g, 0.0050). (Mole), PBOM (14.33 g, 0.044 mol) was added together with 50 g of NMP and reacted at 85 ° C. for 1 hour. Further, as an end-capping agent, 5-norbornene-2,3-dicarboxylic acid anhydride (3.94 g, 0.024 mol) was added together with 10 g of NMP and reacted at 85 ° C. for 30 minutes. After completion of the reaction, the mixture was cooled to room temperature, acetic acid (52.82 g, 0.50 mol) was added together with 87 g of NMP, and the mixture was stirred at room temperature for 1 hour. After completion of stirring, the solution was poured into 3 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed with water three times, and then dried in a ventilation dryer at 50 ° C. for three days to obtain an alkali-soluble polyamide resin (B-4) powder. As a result of evaluation by the above method, the weight average molecular weight of the resin (B-4) was 40,000.

Synthesis Example 11 Synthesis of quinonediazide compound 21.22 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Kagaku Kogyo Co., Ltd.) and 26.86 g (0. 10 mol), 13.43 g (0.05 mol) of 4-naphthoquinonediazide sulfonyl acid chloride was dissolved in 50 g of 1,4-dioxane and brought to room temperature. To this, 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise while being careful not to allow the temperature inside the system to rise above 35 ° C. After the dropping, the mixture was stirred at 30 ° C. for 2 hours. The triethylamine salt was filtered and the filtrate was added to water. Then, the precipitated precipitate was collected by filtration. This precipitate was dried in a vacuum dryer to obtain a quinonediazide compound represented by the following formula.

[ Reference Examples 1 and 2, Examples 3 to 8, Comparative Example 5]
Obtained in (a) 10 g of the resin solution of Synthesis Examples 1 to 6 as the alkali-soluble resin, 5.0 g of the alkali-soluble resin of Synthesis Examples 7 to 10 as the alkali-soluble resin, and (c) Synthesis Example 10 as the photosensitizer. A varnish was prepared by adding 1.2 g of the obtained quinone diazide compound, HMOM-TPHAP (manufactured by Honshu Chemical Industry Co., Ltd.) as a cross-linking agent, and 10 g of GBL as a solvent, and evaluated by the above method.

[Comparative Examples 1 to 4]
(A) As an alkali-soluble resin, 10 g of the resin solution of Synthesis Examples 1 to 6, (c) 1.2 g of the quinone diazide compound obtained in Synthesis Example 10 as a photosensitizer, and HMOM-TPHAP (Honshu Chemical Industry Co., Ltd.) as a cross-linking agent. ), 10 g of GBL was added as a solvent to prepare a varnish, and the evaluation was carried out by the above method.

The composition of the varnish for evaluation is shown in Table 1, and the evaluation results are shown in Table 2.

1 Silicon wafer 2 Al pad 3 Passivation film 4 Insulation film 5 Metal (Cr, Ti, etc.) film 6 Metal wiring (Al, Cu, etc.)
7 Insulating film 8 Barrier metal 9 Scrivener 10 Handa bump

Claims (17)

(A) It has a phenol skeleton and a crosslinkable group having a group selected from the group consisting of a maleimide group, a nadic acid group, an acrylic group, an epoxy group, an alkoxymethyl group and a methylol group (hereinafter referred to as "crosslinkable group"). A resin composition comprising no phenolic skeleton and containing an alkali-soluble resin having a weight average molecular weight in the range of 1,000 to 50,000.
The content ratio of the phenolic skeleton having the crosslinkable group in the total of 100 mol% of the structural units of the phenolic skeleton having the crosslinkable group and the phenolic skeleton not having the crosslinkable group is within the range of 5 to 90 mol%. and in the (a) alkali-soluble resin, have a structure represented by the general formula (1), the general formula a and b in (1), characterized by satisfying the relationship of a> b Resin composition.

(In the general formula (1), R ¹ is a hydrogen atom, a halogen atom, a nitro group, a cyano group, an aliphatic group, an aromatic group, an acetyl group, an ester group, an amide group, an imide group, a urea group, or a thiourea group. the .X represents an organic group having any one of, if .R ¹ and X represents an organic group represented by the following general formula (3) or (4) has a hydrogen atom, the hydrogen atom is a halogen atom, It may be substituted with either a nitro group or a cyano group. Y represents a cross-linking group. A and b are integers of 1 or more, and a + b ≧ 6. The sequence can be blocky or random. ^{M, n 1} , and n ² are integers in the range 1-3. Q is an integer in the range 0-3.)

(In the general formula (3), R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent an aliphatic group having 1 to 10 carbon atoms and may be substituted with a hydrogen atom or fluorine. In the general formula (4), R ⁷ , R ⁸ , R ⁹ and R ¹⁰ independently represent a hydrogen atom, an alkyl group, a fluoroalkyl group, a siloxane group, an alkyl ether group, or a siloxane group. Z represents a hydrogen atom, an alkyl group, a fluoroalkyl group, or a siloxane group. It is a divalent group represented by any one of a single bond, an ether bond, a ketone group, a carbonyl group, an amide group, or a sulfonyl group.) The resin composition according to claim 1, wherein Y in the general formula (1) is an organic group represented by the following general formula (2).

(In the general formula (2), R ² is a hydrogen atom, an aliphatic group, or an aromatic group.) The resin composition according to claim 1 or 2 ^{, wherein n 1} in the general formula (1) is 2 or 3. The resin composition according to any one of claims 1 to 3 , wherein a and b in the general formula (1) satisfy the relationship of 5 ≦ {b / (a + b)} × 100 ≦ 30. Further, it contains one or more kinds of alkali-soluble resins selected from (b) polyimide precursor, polyamide-imide, polyimide, polybenzoxazole precursor, and polybenzoxazole, and the content of the (b) alkali-soluble resin. The resin composition according to any one of claims 1 to 4 , wherein the resin composition is in the range of 1 to 1000 parts by mass with respect to 100 parts by mass of the alkali-soluble resin (a). The resin composition according to claim 5 , wherein the alkali-soluble resin (b) has one or more organic groups selected from an alkyl group, a fluoroalkyl group, an alkyl ether group, and a siloxane group. The resin composition according to claim 5 or 6 , wherein the alkali-soluble resin (b) has a diamine residue having an alkyl ether group. The resin composition according to any one of claims 1 to 7 , further containing (c) a photosensitizer and (d) a cross-linking agent. The resin composition according to any one of claims 1 to 8 , wherein Y in the general formula (1) is an organic group having an acrylic structure. A resin sheet formed from the resin composition according to any one of claims 1 to 9. A cured film obtained by curing the resin composition according to any one of claims 1 to 9. A cured film obtained by curing the resin sheet according to claim 10. A step of applying the resin composition according to any one of claims 1 to 9 on a substrate, or laminating the resin sheet according to claim 10 on a substrate and drying to form a resin film, and a mask. A method for producing a relief pattern of a cured film, which comprises a step of exposing through, a step of eluting or removing an irradiated portion with an alkaline solution to develop the resin film, and a step of heat-treating the developed resin film. The method for producing a relief pattern of a cured film according to claim 13 , wherein the step of applying the resin composition onto a substrate and drying it to form a resin film includes a step of applying the resin composition onto the substrate using a slit nozzle. .. A semiconductor electronic component or semiconductor device in which the cured film according to claim 11 or 12 is arranged as an interlayer insulating film between rewiring. The semiconductor electronic component or semiconductor device according to claim 15 , wherein the rewiring and the interlayer insulating film are repeatedly arranged in 2 to 10 layers. A semiconductor electronic component or semiconductor device in which the cured film according to claim 11 or 12 is arranged as an interlayer insulating film of adjacent substrates made of two or more kinds of materials.

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